JP5121454B2 - Method for producing composite elements based on isocyanate-based foams - Google Patents

Abstract

An apparatus for application of liquids to a continuously conveyed outer layer having a rotating plate which is horizontal and parallel to the outer layer or with a deviation of up to 15° from horizontal, wherein a liquid applied to the rotating plate is ejected centrifugally from the rotating plate via rotation and then, via gravity, passed onto the outer layer below the rotating plate, is provided.

Description

  The present invention relates to a method of producing a composite element comprising at least one outer layer and an isocyanate-based foam using an adhesion promoter.

In particular, the production method of composite elements comprising a metallic outer layer and an isocyanate-based foam (foam), a core part mainly composed of polyurethane (PU) foam or polyisocyanurate (PIR) foam, Is widely practiced on a continuously operated twin belt system (Doppel band unlage) , the element of which is usually called a sandwich element. Along with existing cold insulation sandwich elements, elements with a colored outer layer are always of increasing importance, and they are intended for the formation of front parts in various buildings. The outer layer used here is covered not only with an iron plate but also with a stainless steel plate, a copper plate, and an aluminum plate. The adhesion between the foam and the outer layer is extremely important, especially in the case of frontal elements. If the color of the outer layer is dark, the temperature easily reaches around 80 ° C. even with the outer layer facing away from the heat. If adhesion to the outer layer of the foam is not sufficient, the foam leaves the sheet, creating a blister on the surface, which detracts from the aesthetics of the front part of the building. In order to avoid these problems, a lacquer that promotes adhesion is applied before the manufacture of the coil is completed. However, the method requires that additives such as flow aids, hydrophobizing agents, non-breathing agents, etc. be present in the lacquer that promotes adhesion. These additives sometimes significantly harm the polyurethane formation process. In addition, a reaction takes place in the iron coil between the lacquer on the side facing outwards and the lacquer on the opposite side. Therefore, the additive material transferred to the opposite side most often adversely affects the PU formation process, leading to defects in the sandwich element.

Even prior art corona treatment of the outer layer is not sufficient to remove these defects in many cases. Furthermore, for various reasons, the ideal adjustment of the twin belt temperature for a particular system may be hindered. This is particularly common during the first steps of production. Similarly, this can adversely affect the foam production process and the adhesion of the foam to the metallic outer layer.

  For various reasons, another frequent occurrence in the production of sandwich elements is the undesirable air known as cavities occurring in the lower outer layer and upper outer layer between the steel plate and the rigid polyisocyanurate foam. It is mixing. In particular, when serious temperature changes occur in the application of elements in the front part of a building, this air entrapment between the steel plate and the foam may cause blistering of the steel plate. And this also impairs the beauty of the front part.

As a result, there is a need to find a method that will provide a lasting improvement in the adhesion of PU foam and PIR foam to the metallic outer layer and can also withstand the surrounding environment, which is adversely affected in the production process. The method may be performed in a continuous manner or a batch scheme. As an example, the batch mode of operation may be used during a double belt start-up procedure or may be used while the composite element is being manufactured by a compression means that performs the batch mode. If the PU composition or PIR composition used essentially adheres to the metal outer layer with low adhesion, the use of a continuous system is required.

  At the same time, especially in the lower outer layer, the creation of cavities will be avoided in this way.

  One possible way to improve adhesion is to apply an adhesion promoter to the outer layer. For sandwich elements, the tensile test often determines that the lower outer layer has the lowest adhesion. Furthermore, in the known structure manufactured using sandwich elements, the underside of the metal plate is the outwardly facing surface of the front part of the building and is therefore exposed to harsh environments such as the effects of temperature and suction, The burden is higher than the upper side of the sandwich element. For these reasons, it is possible to apply the adhesion promoter only to the lower outer layer. As soon as the adhesion promoter is applied to the lower outer layer, the PU composition, PIR composition is applied to the outer layer and the structure of outer layer—adhesion promoter—rigid PU / PIR foam—outer layer A composite element is provided.

  There are a variety of established methods for applying lacquers, adhesion promoters, adhesives and thin coatings to common metal plates and other substrates. The lacquer may be applied to the substrate by means of dipping, spraying, electrostatic deposition, plasma coating, flow coating, rolling. Spin coating can also be used to produce a thin film on the substrate. Here, the lacquer is uniformly distributed on the substrate by being applied to the substrate and rotating the substrate. However, this type of method is not practical in the case of metal plates used for the production of sandwich elements.

  Similarly, a rotating device is effectively used in a manner very similar to spin coating, but this lacquer is ejected laterally by centrifugal force by the rotation of the rotating plate. This method is particularly suitable for the coating of external tubes and cavities, as described, for example, in US Pat. No. 3,349,568, DE 2808903, WO9959730. One specific example of this technique is forming and coating with a metal plate. However, in all the methods described in these documents, the coated outer layer is guided around the rotating plate and discharged laterally from the rotating plate by centrifugal force as in the example described in DE 2412686, The lacquer always adheres to the relevant outer layer. In order to improve this adhesion, an electric field was sometimes applied. However, all of these methods can form large amounts of pollutants in the air that are harmful to the environment and health.

The object of the present invention is that since composite elements are generally manufactured by the continuous use of twin belts , adhesion promoters are applied to horizontal metal plates or other outer layers that are continuously transferred horizontally. Finding a suitable method to apply. This eliminates the generation and release of contaminants. Further, the method of applying the adhesion promoter will substantially eliminate the need for maintenance.

  Surprisingly, the above object is achieved by attaching an adhesion promoter to the outer layer by means of a rotating plate placed horizontally, preferably parallel to the outer layer.

  The present invention therefore consists of at least one outer layer a) and a rigid isocyanate-based foam b), between the outer layer a) and the hard isocyanate-based foam b). In which the outer layer a) moves continuously and the adhesion promoter c) and the starting material of the rigid isocyanate-based foam b) are continuous with the outer layer. And applying the adhesion promoter c) using a rotating plate disposed at a horizontal or horizontal position and with an inclination of 15 degrees or less (preferably parallel to the outer layer). A method for the manufacture of a featured composite element is provided.

The present invention further relates to an apparatus for applying a liquid to an outer layer that is continuously conveyed, wherein the liquid is installed in a rotating state in a horizontal state , preferably horizontally and in parallel with the outer layer. The apparatus is characterized in that it is applied to the substrate, discharged from the rotating plate by centrifugal force generated by the rotation of the rotating plate, and sent to the lower outer layer by gravity.

  When the device according to the invention is used for the production of composite elements with isocyanate-based foams, the liquid is preferably an adhesion promoter c).

  The adhesion promoter c) used preferably has a single-component or multi-component polyurethane composition.

The adhesion promoter c) does not yet exceed the air drying time when the starting material of the hard isocyanate based foam b) is applied to the lower outer layer, i.e., hard isocyanate based It has been found useful to have a method characterized in that the reaction of the polyethylene composition is not fully completed at the time when the starting material of foam b) is applied to the lower outer layer . The adjustment in this respect is also made by the distance between the adhesion device for the adhesion promoter and the device for applying the starting material of the rigid isocyanate-based foam b), preferably also by adjusting the reaction of the adhesion promoter. Is called.

  The outer layer used is gypsum board, glass nonwoven fabric, aluminum foil, aluminum plate, copper plate or iron sheet, preferably aluminum foil, aluminum plate or steel plate, particularly preferably iron sheet. Coated or uncoated steel sheets may be used. They are preferably not corona treated.

  The outer layer is transported at a constant speed of 2-15 m / min, preferably 3-12 m / min, particularly preferably 3-9 m / min. In the present invention, the outer layer is preferably positioned horizontally, at least from the time of applying the polyurethane composition b), preferably in all steps from application of the adhesion promoter.

  In conventional sandwich elements, the rigid isocyanate-based foam is closed by upper and lower outer layers. The lower layer is sufficiently adhered by an adhesion promoter.

In the method of the present invention, when a metal plate and foil are used as the outer layer, the outer layer is continuously released from the core, cut and heated, and if necessary with polyurethane. Corona treated to increase coverage, coated with starting material for rigid isocyanate-based foam, so-called PU or PIU composition, cured with twin belts and cut to desired length.

  In principle, adhesion of the adhesion promoter c) can occur in the process at any point between the release of the outer layer and the application with the PU or PIR composition.

  According to the present invention, there should be a slight distance between the application part of the adhesion promoter c) and the application part of the PU composition or PIR composition. This makes it possible to minimize the waste generated at the beginning and end of the process and in the unpredictable reaction of the production process.

The adhesion promoter is ejected from a rotating plate which is disposed horizontally, preferably parallel to the horizontal and lower outer layer and above the lower outer layer, and rotated by driving means. The rotation plate is not good installed below the slope 15 ° from horizontal. The rotating plate may be circular or elliptical. The ratio of length to width is 1 to 1.8, particularly preferably 1 to 1.4, in particular 1.0 to 1.25.

The rotating plate in the rotating state may be completely flat, or the end of the rotating plate may be rounded or angled upward. The end of the rotating plate used is preferably rounded or angled upward. In order to guarantee the discharge of the adhesion promoter c), holes are provided in the corners. The diameter and number of the holes are mutually adjusted as follows: the rotating plate so that the adhesion promoter c) can be dispersed as finely and uniformly as possible in the outer layer located below. All the material supplied above is adjusted so that it is discharged and the maintenance costs of the rotating plate are minimized.

The outer cornered portion is preferably 0.5 to 3 mm in diameter and 4 to 64 holes, preferably 1 to 3 mm in diameter and 12 to 40 holes, preferably 1.5 to 2 in diameter. .5mm with 15 to 30 holes.

As one embodiment, the outer shape of the rotating plate may be a stepped shape. FIG. 1 shows a side view of this type of rotating plate. The staircase shape of the present invention is installed so as to rise outward from the axis of the rotating member (A). There is a hole provided in the rotating plate at the step portion from one step to the adjacent step (B). Thereby, a part of the adhesion promoter c) is discharged to the lower outer layer at the steps of these steps. With this type of rotating plate configured in a staircase shape, in particular, an adhesion promoter is applied uniformly to the outer layer arranged below. Supply of the adhesion promoter to the rotating plate Ru done as close as possible to the rotation axis. Surprisingly, in the present invention, the adhesion promoter is particularly uniformly distributed if the application position of the adhesion promoter parallel to the production direction is exactly before or after the rotation axis. There was found. The diameter of the rotating plate depends on the width of the outer layer, and the diameter is 0.05 to 0.3 m, preferably 0.1 to 0.25 m, particularly preferably 0. 12 to 0.22 m. The rotating plate is installed at a height of 0.02 to 0.22 m, preferably 0.03 to 0.18 m, particularly preferably 0.03 to 0.15 m, from the wet outer layer.

A rotating plate with 2 to 4, preferably 2 to 3, particularly preferably 2 stages is used.

The inclination angle of the hole provided in the rotating plate for discharging the adhesion promoter is about 10 ° to 70 °, preferably 30 ° to 60 ° with respect to the lower outer layer. The hole can be provided in the stepped portion of the staircase or in the outer cornered portion. Here, the number of holes increases from step to step and from the inside to the outside. A hole having a diameter of 1.5 to 2.5 mm in the number of 10 to 30, preferably 12 to 25, particularly preferably 12 to 20, is the bottom of the stepped portion (B) of the step with respect to the rotation axis Is provided. The number of holes in the outermost cornered part (C) is 12 to 40, preferably 12 to 30, particularly preferably 15 to 30, and the diameter of the holes is 1.5 to 2 .5 mm. In the example of a particularly preferred rotating plate, the hole of the squaring portion of the outer is configured to be different inclination relative to the outer layer. The ratio of adjacent step diameters d _n / d _n-1 is 1.2 to 3, preferably 2 to 2.6.

  The wetting radius of the adhesion promoter in the lower outer layer is 0.35 to 0.75 m, preferably 0.25 to 1 m.

  The rotational speed of the rotating plate is preferably 200 to 2500 rpm, particularly preferably 200 to 2000 rpm, and in particular 300 to 1500 rpm.

The amount of adhesion promoter c) applied to the outer layer is 30-300 g / m ² , preferably 40-200 g / m ² , particularly preferably 50-120 g / m ² .

Prior to feeding the adhesion promoter c) to the rotating plate, the adhesion promoter c) is mixed with a high-pressure or low-pressure mixer, preferably a low-pressure mixer, in the machine, and the downstream mixing unit (downstream). applied to the rotating plate by a suitable discharge device such as a mixing unit). If the rotating plate is rotated by the drive means, the adhesion promoter c) is dispersed in an outer layer that is continuously transferred under the rotating plate. As an example, a mixing unit made of resin can be used for mixing and application of an adhesion promoter to a rotating plate. The amount of adhesion promoter c) discharged is so as to obtain the desired amount of the coating per metal plate 1 m ^2, is combined with the speed of the twin-belt operating continuously.

  The height of the rotating plate of the lower outer layer, the diameter of the rotating plate, and its rotating speed are distributed to the end of the steel plate where the discharged adhesion promoter c) moves continuously under the rotating plate. , Compatible with each other in such a way as to give maximum wet uniformity.

  Unlike the prior art, the adhesion promoter c) is ejected laterally by centrifugal force, but under the rotating plate, horizontally, preferably parallel to the rotating plate, as a result of low speed rotation and the influence of gravity. Dispersed in the outer layer. Surprisingly, no air pollutants are produced in the use of the above-described technology.

Here, the air pollutant refers to a colloidal tissue composed of a gas such as small liquid particles having a diameter of about 10 ⁻⁷ to 10 ⁻³ cm.

  From an economic point of view, it is necessary to reduce the amount supplied. For this reason, the lower outer layer cannot be completely wetted (wet) by the adhesion promoter c). However, using the feeding technique of the present invention (to significantly improve the tensile strength between the treated outer layer and the foam located thereon compared to the untreated plate member) It was surprising that the application (feeding) performed on the lower outer layer was found to be sufficient with a small feed rate.

  The method of the present invention can also significantly reduce the proportion of cavities in the lower outer layer.

As soon as the adhesion promoter c) is applied to the lower outer layer, the starting material of the rigid isocyanate foam b) is applied. In the present invention, the adhesion promoter c) is adjusted so that the composition b) and the composition c) are reacted with each other (ie, the starting material of the rigid isocyanate foam b) is applied. The air drying time of c) is not exceeded)
By using the adhesion promoter c), the temperature of the twin belt , which normally reaches 60 ° C. in the course of the PIR composition, can be lowered to 55 ° C.

  FIG. 2 is a side view of the apparatus of the present invention. The adhesion promoter is applied by the metering device (2) of the rotating plate (3) mounted horizontally or preferably parallel to the outer layer (5) and rotated by the driving means (1) and rotated by centrifugal force due to rotation. It is discharged outward from the plate (3) and sent to (5) by gravity.

FIG. 3 is a plan view of a sandwich element manufacturing apparatus used in the present invention. The starting material for the adhesion promoter c) by the rotating plate ( 3 ) and the isocyanate-based foam (b) by the forming portal (6 ) is applied to the lower outer layer ( 5 ).

  The adhesion promoter used is a polyurethane-based adhesion promoter known in the prior art. These are generally obtained by reacting a polyisocyanate with a component having two hydrogen atoms reactive with isocyanate. The ratio of the reaction is preferably such that the ratio of the number of isocyanate groups to the group reactive to isocyanate is 0.8 to 1.8: 1, preferably 1 to 1.6: 1. The reaction rate is selected.

  The polyisocyanates used are conventional aliphatic compounds, cycloaliphatic, in particular aromatic diisocyanates and / or polyisocyanates. Preferably, tolylene diisocyanate (TDI), diphenylmethane diisocyanate (MDI) and special mixed compounds of diphenylmethane diisocyanate and polyphenylene polymethylene polyisocyanate (crude MDI) are used.

  In the present embodiment, preferably, the isocyanate Lupranat (registered trademark of BASF AG) M50, Lupranat (registered trademark of BASF AG) M70, and Lupranat (registered trademark of BASF AG) M200 are used. In one preferred embodiment, the isocyanate used to produce the rigid isocyanate-based foam b) is the same as the isocyanate used to produce the adhesion promoter c). In one preferred embodiment, Lupranat® M70 is used, and in one particularly preferred embodiment, Lupranat® M200 is used.

Compounds used that contain at least two hydrogen atoms that react with isocyanates generally have reactive groups such as OH groups, SH groups, NH groups, NH ₂ groups, acidic CH groups, eg, β-diketone groups. Provide two or more inside.

  Polyethylene and / or polyesterol are preferably used, and polyethylpolyol is particularly preferably used. The hydroxyl number of the polyethylene and / or polyesterol used is preferably 25 to 800 mg KOH / g and the molecular weight is generally above 400. Polyurethanes are prepared without using chain extenders and / or crosslinkers or with chain extenders and / or crosslinkers. In particular, the chain extenders and / or crosslinkers used are difunctional or trifunctional amines and alcohols, in particular diols or triols having a molecular weight of 400 or less, preferably 60 to 300.

  In this embodiment, the viscosity of the polyol component of the adhesion promoter c) is preferably 100 to 1000 mPas, preferably 100 to 800 mPas, particularly preferably 150 to 400 mPas (25 ° C.).

  Where appropriate, the adhesion promoter has an auxiliary or reactive flame retardant. The amount of these commonly used flame retardants is 0.1-30% of the total weight of the polyol component.

  The reaction of the polyisocyanate with the polyol is preferably carried out without using a physical blowing agent. However, the polyol used contains the remaining water which acts as a blowing agent. This results in a concentration of polyurethane adhesion promoter of 200 to 1200 g / liter, preferably 400 to 1000 g / liter, particularly preferably 450 to 900 g / liter.

  The rigid isocyanate-based foam b) used in the process of the invention comprises at least a polyisocyanate and at least reactive with isocyanate groups in the presence of blowing agents, blowing catalysts and customary auxiliaries and / or additives. It is prepared in a conventional and known manner in which a component having two hydrogen atoms is reacted. The following details relate to the starting materials used.

  The organic polyisocyanate used is preferably an aromatic polyfunctional isocyanate.

  Specific examples mentioned are toluene 2,4- and 2,6-diisocyanate (TDI), their corresponding isomeric mixtures, diphenylmethane 4,4 '-, 2,4'- and 2,2'-diisocyanate. (MDI), their corresponding isomer mixtures, mixtures of diphenylmethane 4,4'- and 2,4'-diisocyanate, polyphenylpolymethylene, polyisocyanate, diphenylmethylene 4,4 '-, 2,4'- , And 2,2 ′ diisocyanate and a mixture of polyphenylpolymethylene polyisocyanate (crude MDI), a mixture of crude MDI and toluene diisocyanate. The organic diisocyanate and the polyisocyanate are used individually or mixed.

  Modified polyfunctional isocyanates may be used, i.e. those known as products obtained as organic diisocyanates and / or organic polyisocyanates. Examples include diisocyanates and / or polyisocyanates containing isocyanate groups and / or urethane groups. If appropriate, the modified polyisocyanates can be mixed with each other or with diphenylmethane 2,4-, 4,4-diisocyanate, crude MDI, or toluene 2,4- and / or 2,6-diisocyanate. With an unmodified organic polyisocyanate.

  In the present embodiment, a product of a polyfunctional isocyanate that reacts with a polyhydroxyl group, or a product composed of another dipolyisocyanate and a polyfunctional isocyanate that reacts with a polyisocyanate may be used.

  An organic polyisocyanate that has been found to be particularly suitable is crude MDI containing NCO with a mass percent concentration of 29 to 33% and having a viscosity of 150 to 1000 mPas at 25 ° C.

  Component b) which has at least two hydrogen atoms which are reactive towards isocyanate groups and is used in particular is a polyether alcohol and / or a polyester alcohol with an OH number in the range from 25 to 800 mg KOH / g. is there.

  The polyester alcohol used is usually a polybasic carboxylic acid having 2 to 12 carbon atoms, such as succinic acid, glutaric acid, adipic acid, corkic acid, azelaic acid, sebacic acid, decanedicarboxylic acid, Maleic acid, fumaric acid, preferably phthalic acid, isophthalic acid, terephthalic acid, isomeric naphthalenedicarboxylic acid together with polyhydroxyl alcohol having 2 to 12 carbon atoms, preferably 2 to 6 carbon atoms, preferably Provided by liquefaction of the diol.

  Most of the polyesterols used have 1.5 to 4 functional groups.

  The polyester polyols used in particular are provided by known methods such as, for example, anionic polymerization of alkylene oxides on starting materials having H-functional groups in the presence of catalysts, preferably alkali metal hydroxides. The

  Most often used alkylene oxides are ethylene oxide and / or propylene oxide, preferably pure propylene 1,2-oxide.

  Particularly used starting materials have in the molecule at least 3, preferably 4 to 8 hydroxyl groups or at least 2 primary amino groups. The starting materials used having at least 3 and preferably 4 to 8 hydroxyl groups in the molecule are preferably sugar compounds such as trimethylolpropane, glycerol, pentaerythritol, glucose, sorbitol, mannitol, sucrose, polyhydroxyl Phenols, for example, resols such as oligomer condensates composed of phenol and formaldehyde, Mannich condensates composed of phenol, formaldehyde and dialkanolamine, melamine.

  The starting materials used with at least two primary amino groups in the molecule are preferably phenylenediamine, 2,3-, 2,4-, 3,4- and 2,6-tolylenediamine, And aliphatic di- and polyamines such as 2,2-diaminodiphenylmethane and ethylenediamine, aromatic diamines and / or polyamines.

  The preferred number of functional groups of the polyethyl polyol is 3 to 8, and their preferred hydroxyl number is 25 to 800 mg KOH / g, in particular 240 to 570 mg KOH / g.

  Other components having at least two hydrogen atoms that are reactive towards isocyanates are, where appropriate, cross-linking agents and chain extenders used in combination. It has been found that the addition of bifunctional chain extenders, trifunctional or high functional crosslinkers or, where appropriate, mixtures thereof are useful for modification of mechanical properties. Preferably used chain extenders and / or crosslinkers are alkanolamines and in particular diols and / or triols having a molecular weight of 400 or less, preferably 60 to 300 or less.

  An advantageous use of chain extenders, crosslinkers or mixtures thereof is 1 to 20% by weight, preferably 2 to 5%, based on the polyol component.

  Rigid foams are usually produced in the presence of blowing agents, catalysts, flame retardants, cell stabilizers, and if necessary other adjuvants and / or additives.

  Water may be used as a blowing agent to remove carbon dioxide and react with isocyanate groups. What is known as a physical blowing agent may be used with water, preferably in place of water. These are components that are inert to the starting materials, are almost liquid at room temperature, and evaporate when the urethane reaction occurs. The boiling point of this component is preferably 50 ° C. or lower. Physical blowing agents are also, for example, carbon dioxide, low-boiling alkanes, fluoroalkanes that are gaseous at room temperature and are taken up or dissolved in the starting components under pressure.

  The components are most often alkanes and / or cycloalkanes having at least 4 carbon atoms, dialkyl ethers, esters, ketones, acetals, fluoroalkanes having 1 to 8 carbon atoms, 1 to 3 in the alkyl chain. Selected from the group comprising tetraalkylsilanes, especially tetramethylsilane, having the following carbon atoms:

  Examples mentioned do not damage the propane, n-butane, isobutane, cyclobutane, n-pentane, isopentane, cyclopentane, cyclohexane, dimethyl ether, methyl ethyl ether, methyl butyl ether, methyl formate, acetone, and the ozone layer. Fluoroalkanes separated in the troposphere, such as trifluoromethane, difluoromethane, 1,1,1,3,3-pentafluorobutane, 1,1,1,3,3-pentafluoropropane, 1,1,1 2-tetrafluoroethane, difluoroethane, heptafluoropropane. The physical blowing agents described above can be used alone or in any desired combination with each other.

  The polyisocyanurate foam or polyisocyanurate foam usually contains a flame retardant. It is preferable to use a flame retardant that does not contain bromine. It is particularly preferred to use a flame retardant containing phosphorus atoms, in particular trischloroisopropyl phosphate, ethane diethylphosphonate, triethyl phosphate and / or diphenyl cresyl phosphate.

  Particularly used catalysts are those that significantly accelerate the reaction between isocyanate groups and groups that are reactive with isocyanate groups. Such catalysts are, for example, strongly basic amines such as secondary aliphatic amines, imidazoles, amidines, alkanolamines and / or organometallic components, in particular based on tin.

  If the isocyanurate group is incorporated into a rigid foam, a specific catalyst is required. The isocyanurate catalyst used is usually a metal carboxylate, in particular potassium acetic acid and its solution. The catalyst may be a single or a mixture mixed with each other as required.

  Adjuvants and / or additives used for this purpose are, for example, surfactants, foam stabilizers, foam regulators, fillers, pigments, dyes, hydrolysis stabilizers, antistatic agents, fungistatic agents And substances known per se such as bacteriostatic preparations.

  Furthermore, details relating to the implementation of the method of the invention, starting materials used, blowing agents, catalysts, adjuvants and / or additives can be found by way of example in Kunststoffhandbuch [Plastic Handbook], volume 7, “Polyuretanes” [“Polyethanes”. Carl-Hanser-Verlag Munich, 1st edition, 1966, 2nd edition, 1983, and 3rd edition, 1993.

  In order to produce a rigid isocyanate-based foam, the polyisocyanate and the component having at least two hydrogen atoms that react with isocyanate groups have an isocyanate index of 100 to 220, preferably 115 to 180, in the case of polyisocyanurate foams. It reacts to become. Rigid polyisocyanurate foams may be produced batchwise or continuously using known mixing equipment.

  With an index greater than 180, preferably an index between 200 and 500, particularly preferably between 250 and 500, operations for the production of polyisocyanurate foams are also possible.

  Inventive rigid PU foams are usually produced by a two-component process. In this method, when a component having at least two hydrogen atoms reactive to an isocyanate group is mixed with a blowing agent, a catalyst, and other auxiliary agents and / or additives, a component known as a polyol component This component reacts with polyisocyanate or, where appropriate, mixed components also called polyisocyanate and the isocyanate component of the blowing agent.

  The starting components are usually mixed at 15 ° C to 35 ° C, preferably 20 ° C to 30 ° C. The reaction mixture may be mixed by using a high or low pressure supply machine.

The density of the rigid foam used for this purpose is preferably 10 to 400 kg / m ³ , preferably 20 to 200 kg / m ³ , in particular 30 to 100 kg / m ³ .

  The thickness of the composite element is usually 5 to 250 mm.

A) Synthesis of adhesion promoter composition A component 62 parts by mass of polyetherol 1 having propylene glycol and propylene oxide as components, functional group 2, hydroxyl value 250 mgKOH / g
25 parts by mass of polyesterol 1, whose component is phthalic anhydride, diethylene glycol, oleic acid, functional group 1.8, hydroxyl value 200 mgKOH / g
10 parts by mass of tris chloroisopropyl phosphate flame retardant, TCPP
2 parts by mass is a silicone-containing stabilizer 1 part by mass is an amine-containing PU catalyst B component Isocyanate Lupranat M50, polymer MD (BASF AG)
The A component and the B component are mixed with each other at a ratio such that the index is about 115. There is no additional blowing agent added. However, the polyol used contains residual water and the resulting concentration of the cured adhesion promoter is on the order of about 560 g / liter.

B) Synthesis of PU composition II A component 55.5 parts by mass of polyetherol 1 having sorbitol and propylene oxide as components, functional group 5, hydroxyl value 500 mgKOH / g
20 parts by mass of flame retardant 1 (triscoloroisopropyl phosphate, TCPP)
20 parts by mass of flame retardant 2 (PHT-4-diol (Lake Great))
1.5 parts by weight of silicone-containing stabilizer 3 parts by weight of catalyst 1 (amine-containing PU catalyst)
Blowing agent 1n-pentane Blowing agent 2 water B component Isocyanate Lupranat M50, polymer MD (BASF AG)
The A component, the B component, and the foaming agent react so that the coating density achieved at an index of about 130 is about 43 g / L.

C) Synthesis of PIR composition A component 56 parts by mass of polyesterol 1, whose component is phthalic anhydride, diethylene glycol and oleic acid, functional group 1.8, hydroxyl value 200 mgKOH / g
10 parts by mass of polyetherol 1 having ethylene glycol and ethylene oxide as components, functional group 2, hydroxyl value 200 mgKOH / g
30 parts by mass of flame retardant 1 (Triscolloisopropyl phosphate, TCPP)
1.5 parts by weight of stabilizer 1 (silicone-containing stabilizer)
1.5 parts by mass of catalyst 1 (PIR catalyst, carboxylate)
1 part by mass is catalyst 2 (amine-containing PU catalyst)
Foaming agent 1: n-pentane Foaming agent 2: Water B component Isocyanate Lupranat M50, polymer MD (BASF AG)
The A component, the B component, and the foaming agent are mixed with each other so that the coating density achieved at an index of about 350 is 43 g / liter.

The adhesion promoter composition is mixed in a low pressure mixing machine (Unipre) at a slightly elevated temperature, 30 ° C. to 50 ° C., and applied to the rotating plate by a plastic mixing facility. The diameter of the rotating plate is 15cm, and a squaring been end. Height of the squaring portion is 15 mm. In the vicinity of the end portion, 32 holes are provided, and the adhesion promoter composition is discharged by centrifugal force through the hole. The rotation speed is 900 rpm. The width of the twin belt is 1.2 m, and the twin belt is operated at a speed of 3 m / min. The amount of adhesion promoter discharged is varied according to the amount it is applied, 60, 80, 100 g / m ² . The temperature of the twin belt varies between 55 ° C and 60 ° C.

  The above adhesion promoter composition c) is applied 2 m upstream of the foaming start point. The polyisocyanurate system b) is applied by means of a vibration application bar having a plurality of nozzles. The metal outer layer is not corona treated. Once the composition is cured, test specimens with a capacity of 100 × 100 × 5 mm are identified and the adhesion of the foam to the outer layer is determined according to DIN EN ISO 527-1 / DIN 53292.

  The number of cavities is determined visually.

  Table 1: Experimental parameters and results

  Examples 5 and 6 are comparative examples of products of sandwich elements in which no adhesion promoter is used.

  The example of the rotating plate is variously modified to maximize the uniformity of adhesion promoter distribution in the lower rotating layer.

  Table 2: The shape of the rotating plate used and the observed distribution of the adhesion promoting composition c) on the outer layer to be coated

  The table evaluates that the application of the adhesion promoter to the surface of the outer layer is uniform. If the application is not uniform, most of the composition c) accumulates at the edges of the outer layer.

It is a side view of an example of the rotating plate in the present invention. It is a side view of the manufacturing apparatus of the sandwich element of this invention. It is a top view of the manufacturing apparatus of the sandwich element of this invention.

Claims (24)

A composite element comprising at least one outer layer a) and a hard isocyanate-based foam b), wherein an adhesion promoter c) is applied between the outer layer a) and the hard isocyanate-based foam b). A manufacturing method of
The outer layer a) is continuously moved, the adhesion promoter c) and the starting material of the rigid isocyanate-based foam b) are continuously applied to the outer layer, and the adhesion promoter c) is foamed. In a state adjusted to react with the body b), applied by a rotating plate in a rotating state arranged at a horizontal or horizontal position and an inclination of 15 degrees or less,
A process for producing an isocyanate-based composite element, characterized in that the adhesion promoter c) is a liquid and is supplied to a rotating plate . The adhesion promoter c) used is
2. The method of claim 1 comprising constituting a single or multiple component reactive polyurethane composition.   3. A method according to claim 2, wherein the starting material of the rigid isocyanate-based foam b) is applied to the lower outer layer before the adhesion promoter c) exceeds its air drying time. . The concentration of the adhesion promoter c) is
Method according to claim 2, characterized in that it is 200-1200 g / L. The adhesion promoter c)
3. A method according to claim 2, which does not contain a physical blowing agent. The rigid isocyanate-based foam b)
The method according to claim 1, which is a polyurethane foam or a polyisocyanurate foam. The outer layer used is
Gypsum board, the method according to claim 1, wherein the glass non-woven fabric, aluminum foil, aluminum plate, a copper plate or iron sheet der Rukoto. The method according to claim 1, wherein the outer layer used comprises a steel plate.   The method according to claim 1, characterized in that the temperature of the twin belt system used for the production of the composite element is less than 60C. The method according to claim 1, wherein the amount of adhesion promoter c) applied to the outer layer is 30-300 g / m ² .   The method according to claim 1, wherein the wetting of the outer layer to which the adhesion promoter c) has been applied may not be complete.   The method of claim 1, wherein the outer layer is transported at a constant speed of 2 to 15 m / min.   The method of claim 1, wherein the rotating plate is circular.   The method of claim 1, wherein the rotating plate is elliptical.   The method according to claim 1, wherein an outer shape of the rotating plate is a stepped shape.   The method according to claim 1, wherein a ratio of a length to a width of the rotating plate is 1 to 1.8. The diameter of the rotating plate is
The method according to claim 1, wherein the length is 0.05 to 0.3 m based on the longitudinal direction.   The method of claim 1, wherein the rotating plate is completely flat. The method according to claim 1, wherein the end of the rotating plate has a shape that is rounded upward or rounded . 20. A method according to claim 19, characterized in that 4 to 64 holes having a diameter of 0.5 to 3 mm are provided in the outer rounded or angled part. The outer shape of the rotating plate is a staircase shape,
The method according to claim 19, wherein 10 to 30 holes having a diameter of 1.5 mm to 2.5 mm are installed in a stepped portion of each staircase.   The method according to claim 1, wherein the rotating plate is placed 0.02 to 0.2 m above the wet outer layer.   The method according to claim 1, wherein the wet radius of the adhesion promoter c) on the outer layer a) is 0.25 to 1 m.   The method according to claim 1, wherein the rotational speed of the rotating plate is 200 to 2500 rpm.

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